Methoxy carboxylic acid ester ultraviolet stabilizers for polymers

ABSTRACT

WHERE R8 is hydrocarbyl, m is 1 to 4, n is 0 or 1 and m+n is 1 to 4;   WHERE R12 is lower alkyl and G is H or   AND WHERE AT LEAST ONE OF THE N&#39;&#39;S IS ZERO.   WHERE S IS 1 TO 3 AND T IS FROM 0 TO 2, THE TOTAL OF S AND T BEING NOT OVER 3; (D) Compounds of the formula   ARE PREPARED AND ARE USED AS ULTRAVIOLET LIGHT AND WEATHERING STABILIZERS FOR POLYMERS, PREFERABLY POLYPROPYLENE. In the formula R is alkoxyphenyl, dialkoxyphenyl or alkylene dioxyphenyl, the alkoxy groups have 1 to 8 carbon atoms and the alkylene group has 1 to 4 carbon atoms, q is 1 to 6, and Z is   WHERE R&#39;&#39; is H or a 1 to 4 carbon alkyl, R7 is hydrogen or

United States Patent Gough June 10, 1975 METHOXY CARBOXYLIC ACID ESTER [56] References Cited ULTRAVIOLET STABILIZERS FOR UNITED STATES PATENTS POLYMERS 2,964,494 12/1960 Lappin et al 260/459 75 lnventor; R b G h Ci i i Ohi 3,022,268 2/1962 Armitage et a1. 260/4585 3,031,506 4/l962 Fuson et a1. 260/3403 [73] Assigneez Cincinnati Mllacron Inc., 3,285,855 11/1966 Dexter et a1. 260/4585 Cincinnati, Ohio 3,677,965 7/1972 Dexter et a1. 260/459 Filed: J 1974 3,717,611 2/1973 Baumer et al. 260/4595 21 A l N 431 913 FOREIGN PATENTS OR APPLICATIONS 1 PP- 1 1,292,603 3/1962 France 260/459 Related US. Application Data [62] Division Of Ser. NO. 297,446, 061. 13, 1972, Pat. NO. Primary Examinekvr Hoke 3,814,729. Attorney, Agent, or FirmCushman, Darby &

Cushman [52] US. Cl. ..260/45.8 A; 260/45.85 R;

260/45.9 NC ABSTRACT [51] Int. Cl. C08f 45/60 Compounds which are methoxy carboxylic acid esters Field of Search 260/473 45.8 are employed as ultraviolet light stabilizers.

22 Claims, N0 Drawings This is a division of application Ser. No. 297,446, filed Oct. 13, 1972, now U.S. Pat. No. 3,814,729.

The present invention relates to compounds useful as stabilizers for polymers. They are particularly useful in stabilizing olefin polymers, especially propylene polymers against degradation resulting from exposure to ultraviolet radiation and/or weathering conditions. It is well known that many organic polymeric materials undergo deterioration upon exposure to ultraviolet radiation. Light having wavelengths in the region 290-400 nanometers causes photocatalyzed changes, such as yellowing or embrittlement, in unstabilized polymers. To overcome this problem it is usually necessary to stabilize the polymeric materials if they are to be formed into objects which will be subjected to sunlight or ultraviolet radiation, during use. Normally this stabilization is achieved by incorporation of chemical compounds as additives into the polymeric material.

It is, therefore, an object of the present invention to provide polymeric compositions which contain esters or amides of various alkoxy and dialkoxybenzoic acids with alcohols, preferably polyfunctional alcohols, or polyfunctional amines and which are substantially resistant to ultraviolet deterioration.

Another object is to prepare polymeric compositions which are more resistant to weathering conditions.

A more specific object is to stabilize polypropylene and other propylene containing polymers against degradation due to exposure to ultraviolet light and/or weathering.

Other objects will become apparent hereinafter.

In accordance with the present invention, it has been discovered that a substantial increase in resistance to ultraviolet light deterioration and weathering conditions of polymers, especially polypropylene are obtained when there is incorporated into the polymer composition esters or amides of the formula In the formula R is alkoxyphenyl, dialkoxyphenyl or alkylene dioxyphenyl, the alkoxy groups have 1 to 8 carbon atoms, and the alkylene group has 1 to 4 carbon atoms, q is l to 6, Z is where R is H or a 1 to 4 carbon alkyl, R is hydrogen or where R is hydrocarbyl, m is l to 4, n is 0 or 1 and m+n is 1 to 4; 4

(G) O-CH HC-O- (G) n where R is lower alkyl and G is H or and where at lease one of the ns is zero.

(Ho) o s where s is l to and t is from O to 2, the total ofs and 2 being not over 3;

where v and w are each 1 to 4 and p is 2 to 4;

where x is 2 to 3; (j) alkoxy of 1 to 18 carbon atoms; (k) NHR where R is 1 to 18 carbon atom alkyl or H;

where Y is O,R Owhere R is an alkylene of l to 3 carbon atoms,

and f is 2 to 4;

Preferably the esters are esters of pentaerythritol. R is preferably dialkoxyphenyl, more preferably dimethoxyphenyl, most preferably 3,4-dimethoxyphenyl.

Among the compounds employed in the invention are the following when Z is (a): pentaerythritol tetra (3,4-dimethoxybenzoate) (pentaerythritol tetra veratrate), pentaerythritol tetra (2,4-dimethoxy benzoate), pentaerythritol tetra (3,5-dimethoxybenzoate), pentaerythritol tetra (3methoxy-4-butoxybenzoate), pentaerythritol tetra (3methoxy-4-octoxybenzoate), pentaerythritol tetra (3-methoxy-5-octoxybenzoate), pentaerythritol tetra (2-methoxy-4-isopropoxybenzoate), pentaerythritol tetra (3,4-diethoxybenzoate), pentaerythritol tetra (3,4-dioctoxy benzoate), pentaerythri tol monostearate tris (3,4-dimethoxybenzoate), pentaerythritol monostearate tris (2,4-dimethoxybenzoate), pentaerythritol monostearate tris (3,5-dimethoxybenzoate), pentaerythritol monostearate tris (3 methoxy-4-pentoxybenzoate pentaerythritol monobenzoate tris (3,4-dimethoxybenzoate), pentaerythritol monooleate tris (3,4-dimethoxybenzoate), pentaerythritol monoacetate tris (3,4-dimethoxybenzoate), pentaerythritol monolaurate tris (2,4-dimethoxybenzoate), pentaerythritol monopalmitate tris (3 ,5 dimethoxybenzoate pentaerythritol tris (3,4-dimethoxybenzoate), pentaerythritol monohexanoate bis (3,5-dimethoxybenzoate), pentaerythritol propionate tris (3,4-dimethoxybenzoate), pentaerythritol tetra (4-methoxybenzoate), pentaerythritol tetra (4-ethoxybenzoate pentaerythritol tetra (4- octoxybenzoate), pentaerythritol tetra (3- methoxybenzoate pentaerythritol tetra (2- tris methoxybenzoate), pentaerythritol tris (4- methoxybenzoate), pentaerythritol monostearate tris (3-butoxybenzoate pentaerythritol monomyristate (2-methoxybenzoate), pentaerythritol tetra (2,3-methylenedioxybenzoate), pentaerythritol (3 ,4methylenedioxybenzoate), pentaerythritol (3,4-ethylenedioxybenzoate), 1,1,1-trimethylol propane tris (3,4-methylenedioxybenzoate), 1,1,1- trimethylolethane tris (3,4-methylenedioxybenzoate), 1,1,1-trimethylolbutane tris (3,4-dimethoxybenzoate), 1,1,1-trimethylolethane tris (3,4-dimethoxybenzoate), 1,1,1-trimethylolpropane tris (3,4-dimethoxybenzoate), 1,1,1-trimethylol propane tris (3,5-dimethoxybenzoate), 1,1,1-trimethylol ethane tris (2,4-dimethoxybenzoate), 1,1,l-trimethylo1 ethane tris (3methoxy-4-hexoxybenzoate), 1 ,1 ,1- trimethylolpropane tris (4-methoxybenzoate), 1,1,1- trimethylolpropane monostearate bis (3,4-dimethoxybenzoate), 1,1,1-trimethylolethane bis (3,4-dimethoxybenzoate), glycerol tris (3,4-dimethoxybenzoate); when 2 is (b):

methyl-alpha-D-glucoside tetra (3,4-dimethoxybenzoate), methyl-beta-D-gluoside tetra (3,4-dimethoxybenzoate), methyl-alpha-D-glucoside tri (3,4-dimethoxybenzoate), methyl-alpha-D-glucoside tetra (3 ,S-dimethoxybenzoate methyl-alpha-D-glucoside tetra (3methoxy-4-octoxybenzoate), methyl-alpha-D- glucoside tetra (2,4-dimethoxybenzoate), methylalpha-D-glucoside tetra (4-methoxybenzoate), methylalpha-D-glucoside tetra (3-methoxybenzoate), methylalpha-D-glucoside tetra (2-methoxybenzoate), methylalpha-D-glucoside tetra (3,4-methylenedioxybenzoate), methyl-alpha-D-glucoside tetra (3,4-ethylenedioxybenzoate), methyl-alpha-D-glucoside monoacetate tris (3 ,4-dimethoxybenzoate methyl-alpha-D- glucoside tetra (2,4-diethoxybenzoate), ethyl-alpha-D- glucoside tetra (3,4-dimethoxy benzoate), propylalpha-Diglucoside tetra (2-methoxy-4-octoxy benzoate), butyl-alpha-D, glucoside tetra (3,4-dimethoxy benzoate), when Z is (c):

1,2-cyclohexanediol di (3,4-dimethoxybenzoate) 1,2-cyclohexanediol di(3,5-dimethoxybenzoate), 1,2-

cyclohexanediol di (2,4-dimethoxybenzoate 1 ,2- cyclohexanediol di (Z-methoxybenzoate l ,2- cyclohexanediol di (3 methoxybenzoate 1 ,2- cyclohexanediol di (4-methoxybenzoate 1 ,2-

cyclohexanediol di (2,3methylenedioxybenzoate, 1,2- cyclohexanediol di(3,4-methylenedioxybenzoate), 1,2- cyclohexandiol di(3,4-ethylenedioxybenzoate), 1,3- cyclohexanediol di (3,4-dimethoxybenzoate), 1,4- cyclohexanediol di (3,4-dimethoxybenzoate), 1,2,4- cyclohexanetriol tri (3,4-dimethoxybenzoate), 1,2,4- cyclohexanetriol mono (3,4-dimethoxybenzoate l ,2,4-cyclohexanetriol di( 3 ,4-dimethoxybenzoate l ,2-cyclohexanediol di butoxybenzoate); when Z is (d):

ethylene glycol di (3,4-dimethoxybenzoate), ethylene glycol di (2,4-dimethoxybenzoate), ethyleneglycol di (3,5-dimethoxybenzoate), ethylene glycol di (4- methoxybenzoate), ethylene glycol di (2- methoxybenzoate), ethylene glycol di (3-methoxy-4- octoxy-benzoate), ethylene glycol di (2,3-methylene dioxybenzoate), ethylene glycol di (3,4-methylene dioxybenzoate), propylene glycol di (3,4-dimethoxybenzoate), propylene glycol di (Z-methoxybenzoate), propylene glycol di (3,4-methylenedioxybenzoate), trimethylene glycol di (3,4-dimethoxybenzoate), ethylene glycol di (3-methoxy-4-octoxy-benzoate), hexamethylene glycol di (3,4-dimethoxybenzoate);

when Z is (e): mannitol hexa (3,4-dimethoxy benzoate), mannitol penta (3,4-dimethoxy benzoate), sorbitol hexa (3,4- dimethoxy benzoate), sorbitol penta (3,4-dimethoxy benzoate), rhamnitol penta (3,4-dimethoxy benzoate), arabitol penta (3,4-dimethoxy benzoate), Xylitol penta (3,4-dimethoxy benzoate), mannitol monostearate penta (3,4-dimethoxy benzoate), and sorbitol hexa (4- methoxy benzoate). 1,2,6-hexanetriol tris (3,5-dimethoxybenzoate), l,2,6-hexantriol tris (3,4-dimethoxybenzoate l ,2,6-hexanetroil tris (4- methoxybenzoate);

when Z is (f):

1,2-bis (3,4-dimethoxybenzamido)benzene,

(3-methoxy-4- OCH 0 o 3 CH O -NH NH- 3 l,2-bis (3,5-dimethoxylbenzamido) benzene, l,2-bis (2,4-dimethoxybenzamido) benzene, 1,2-bis (4- methoxybenzamido) benzene, 1,2-bis (3-methoxybenzamido)benzene, 1,2-bis (Z-methoxybenzamido) benzene, 1,2-bis (3,4-methylenedioxybenzamido)benzene,

1,2-bis (3-methoxy-4-octoxy-benzamido) benzene, 1,2-4-tris, (3,4-dimethoxybenzamido )benzene, 3,5- dimethoxybenzamido-benzene, 3 ,4-

(4-methoxybenzamido) cyclohexane, 1,2-bis (3- methoxybenzamido) cyclohexane, l ,2-bis( 2- methoxybenzamido )cyclohexane, l,2-bis (3 ,4- methylenedioxybenzamido )cyclohexane, 1,2-bis (3-methoxy-4-octoxy-benzamido) cyclohexane,l ,2,4-

tris (3,4-dimethoxybenzamido)cyclohexane, 3,5- dimethoxybenzamido cyclohexane, 3,4- dimethoxybenzamido cyclohexane, 2-

methoxybenzamido cyclohexane;

when Z is (h):

beta-( 3,4-dimethoxybenzamido)ethyl veratrate 0 ClI Cli Nll C OCH II o 3,4-dimethoxybenzamido methyl veratrate, gamma- (3,4-dimethoxybenzamido)propyl veratrate, delta- (3 ,4-dimethoxybenzamido )butyl veratrate beta-3-methoxybenzamidoethyl veratrate, beta-(3- methoxy-4-octoxybenzamido)ethyl veratrate, beta-(3,4-dimethoxybenzamido) ethyl-3-methoxy-4- octoxybenzoate; when Z is (i):

1,2-xylylene glycol di (3,4-dimethoxybenzoate), 1,2-

xylylene glycol di (3,5-dimethoxybenzoate), 1,2-xylene glycol di (2,4-dimethoxybenzoate), 1,2-xylylene glycol di (2-methoxybenzoate), 1,2-xylylene glycol di (3-methoxy-4-octoxybenzoate), 1,2-xylylene glycol di (3,4-methylenedioxybenzoate), 1,4-xylene glycol di (3,4-dimethoxybenzoate), 1,3-xylylene glycol di (3,4-dimethoxybenzoate), l ,2- benzeneditetramethylene glycol bis (3,4-dimethoxybenzoate), l,2-cyclohexanedimethanol bis (3,4-dimethoxybenzoate), l,2-cyclohexanedimethanol bis (4- ethoxybenzoate), 1,2-cyclohexanedimethanol-bis(3,4- methylenedioxybenzoate), l ,4- cyclohexanedimethanol-bis-(3,4-dimethoxybenzoate), l,2,4-benzenetrimethanol-tris(3,4-dimethoxybenzoate);

when Z is (1'):

methyl veratrate, ethyl veratrate, propyl veratrate, butyl veratrate, t-butyl veratrate, octyl veratrate, decyl veratrate, octadecyl veratrate, methyl 2,4-dimethoxybenzoate, ethyl 2,4-dimethoxybenzoate, butyl 2,4-dimethoxybenzoate, methyl 3,5-dimethoxybenzoate, methyl 4-methoxybenzoate, propyl Z-methoxy benzoate, octyl-3-methoxybenzoate, methyl-4- octoxybenzoate, ethyl 3-methoxy-4-octoxybenzoate;

when Z is (k):

3,4-dimethoxybenzamide, N -methyl-3,4-dimethoxybenzamide, N-octyl-3,4-dimethoxybenzamide, N- octadecyl-3,4-dimethoxybenzamide, N-ethyl-3,5-dimethoxybenzamide, N-propyl-2,4-dimethoxybenzamide, N-methyl-3-methoxy-4-octoxybenzamide, N-hexyl-4-methoxy-benzamide, N-octyl-Z- methoxybenzamide, N-methyl-3,4-methylenedioxybenzamide; and

when Z is (l):

1 ,2-cyclopentanediol diveratrate, l ,2- cyclopentanediol di(2,4-dimethoxybenzoate), 1,2-

cyclopentanediol di (3 ,4-methylenedioxybenzoate l,2-cyclopentanediol di (3-methoxy-4- octoxybenzoate l ,3-cyclopentanediol dive ratrate,

1,2-cyclopentanediol di (4-methoxybenzoate), 1,2- cyclopentanedimethanol di (3,4-dimethoxybenzoate), l,2-cyclopentanedipropanol di (2,4-dirnethoxybenzoate), 1,2,4-cyclopentanetriol triveratrate, N,N'-bis (3,-

RC Hal where Hal is chlorine or bromine with the appropriate monohydric or polyhydric alcohol or phenol, e.g., pentacrythritol, methylalpha-D-glucose, 1,2,6-hexanetriol, ethylene glycol, propylene glycol, mannitoL sorbitol,

rhamnitol, arabitol, xylitol, hexamethylene, glycol, l, l,

l-trimethylolethane or 1, l, l-trimethylol propane, methyl alcohol, t-butyl alcohol, octyl alcohol, octadecyl alcohol, 1,2-cyclohexanediol, resorcinol, hydroquinone, xylylene glycol, 1,2-cyclopentanediol. Similarly the amides, can be prepared in conventional fashion by reacting stoichiometric amounts of an acyl chloride (or bromide) of the formula RC Hal with a mono or polyamine such as l,2-phenylene diamine, 1,4-phenylene diamine, l,2-xylylene diamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2,4-benzene-triamine, methylamine, octylamine, ethylamine.

In making the esters and amides in place of the acyl halides there can be used the corresponding acids and salts, e.g., veratric acid and sodium veratrate.

Beta (3,4-dimethoxybenzamido) ethyl veratrate is made by reacting stoichiometric amounts of hydroxyethylamine and veratroylchloride in a conventional manner.

The compounds of the invention are compatible with olefin polymers and significantly stabilize olefin polymers against the deteriorating effects of ultraviolet light without causing undesirable discoloration of the polymers.

While not being limited by theory it is believed that the present compounds work on a different principle. Ultraviolet stabilizers previously known in the art are commonly believed to function by intramolecular photoisomerizations which are reversible, or by quenching electronically excited chromophores in the polymer substrate. lt is generally known that certain molecules when electronically excited can be deactivated or quenched by other molecules, and in some cases there is no net chemical change in either quencher or quenchee. Fuurther it is known that the quenching process requires the quenchee and quencher to collide or at least be less than 100A apart. We believe the compounds disclosed in this application function as ultraviolet stabilizers because they contain ultraviolet absorbing groups (quenchees) which are held in close proximity to quenching groups so that collison or very close approach between quencher and quenchee can occur almost instantaneously after electronic excitation. The quencher and quenchee are held in close proximity by means of chemical bonds or by attractive forces such as hydrogen-bonding, dipoledipole interaction, or electrostatic attraction.

This mechanism as stated is different than that of normal stabilization. The effect of the use of the compounds of the invention is to inhibit polymer degradation because it takes the energy first before it attacks the polymer molecule.

While the ultraviolet light stabilizers of the present invention are most useful as ultraviolet light stabilizers for polypropylene and propylene copolymers with othe hydrocarbons their utility is not limited thereto.

The ultravioletlight stabilizers of the present invention are particularly effective with solid polyethylene, polypropylene, ethylene propylene copolymers (e.g., 50:50, :20 and 20:80), ethylene monoolefin copolymers wherein the monoolefin has 4-10 carbon atoms and is present in a minor amount, e.g., ethylenebutene-l copolymer (95:5) and ethylene-decene-l copolymer (:10). Furthermore, they can be used to stabilize natural rubber, styrene-butadiene rubber (SBR). e.g. (75% butadiene-25% styrene), EPDM rubbers, ABS terpolymers (e.g., 20-30% acrylonitrile, 20-30% butadiene, 40-60% styrene), polyisoprene polybutadiene, butyl rubber, and butadiene-acrylonitrile (e.g., 60:40).

, As the EPDM rubber there can be employed many of the commercially available EDPM rubbers. The EPDM rubber normally contains 30 to 70 molar percent (preferably 50 to 60 molar percent) of ethylene 65 to 20 molar percent (preferably 35 to 45 molar percent) propylene and l to 15 molar percent (preferably 3 to 5 molar percent) of the nonconjugated polyolefin. Usually the polyolefin is not over 10 molar percent. The

I ethylene and propylene can each be 5 to molar percent'of the composition.

As used in the present specification and claims, the term nonconjugated polyolefin includes aliphatic nonconjugated polyene hydrocarbons and cycloaliphatic nonconjugated polyene hydrocarbons, e.g., endocyclic dienes. Specific examples of suitable nonconjugated polyolefins include pentadiene-l,4; hexadiene-l,4; dicyclopentadiene, methyl cyclopentadiene dimer, cyclododecatriene, cyclooctadiene-l,5; 5-methylene-2- norborene.

Specific examples of suitable terpolymers are the Royalenes which contain 55 mole percent ethylene, 40 to 42 mole percent propylene and 3 to 5 mole percent dicyclopentadiene; Enjay terpolymers, e.g., ERP-404 of Enjay and Enjay 3509 which contains about 55 mole percent ethylene, 41 mole percent propylene and 4 mole percent 5-methylene-2-norbornene; Nordel, a terpolymer of 55 mole percent ethylene, 40 mole percent propylene and 5 mole percent hexadiene-l ,4. Another suitable terpolymer is the one containing 50 mole percent ethylene, 47 mole percent propylene and 3 mole percent 1,5-cyclooctadiene (Dutrel).

Examples of EPDM rubbers are given in U.S. Pat. Nos. 2,933,480; 3,000,866; 3,063,973; 3,093,620; 3,093,621, and 3,136,379, in British Pat. No. 880,904 and in Belgium Pat. No. 623,698.

There can be incorporated conventional phosphites in an amount of 0.1 to 10 parts per 1000 parts of polymer. Typical of such phosphites are triphenyl phosphite, tris decyl phosphite, decyl diphenyl phosphite, di(p-t-butylphenyl) phenyl phosphite, di-phenyl-ocresyl phosphite, trioctyl phosphite, tricresyl phosphite, tri-benzyl phosphite, polymeric phosphites such as the one prepared from triphenyl phosphite and hydrogenated bisphenol A and having a molecular weight of about 3000 and (a linear polymeric pentacrythritol hydrogenated bisphenol A phosphite made in accordance with US. Pat. No. 3,053,878, distearyl pentaerythritol diphosphite, thiophosphites such as trilauryl trithiophosphite, trioleyl trithiophosphite and tristearyl trithiophosphite.

There can also be included thio compounds conventionally employed in monoolefin polymers formulations, e.g., in an amount of 0.01 to 10%, usually 0.1 to 5% of the polymer. Thus, there can be used pentaerythritol tetra (mercaptoacetate), l l l -trimethylolethane tri (mercaptoacetate), 1,1,1-trimethylolpropane tri (mercaptoacetate), dioleyl thiodipropionate, dilauryl thiodipropionate, other thio compounds include distearyl 3,3'-thiodipropionate, dicyclohexyl-3,3'-thiodipropionate, dicetyl-3,3'-thiodipropionate, dioctyl-3,3'-thiodipropionate, dibenzyl-3,3'-thiodipropionate, lauryl myristyl-3 ,3 '-thiodipropionate, diphenyl-3 ,3 -thiodipropionate, di-p-methoxyphenyl-3,3-thiodipropionate, didecyl-3,3'-thiodipropionate, dibenzyl-3,3'-thiodipropionate, diethyl-3,3'-thiodipropionate, lauryl ester of 3-methyl-mercapto propionic acid, lauryl ester of 3-butyl-mercapto propionic acid, lauryl ester of 3- laurylmercapto propionic acid, phenyl ester of 3- octylmercapto propionic acid, lauryl ester of 3- phenylmercapto propionic acid, lauryl ester of 3-benzyl-mercapto propionic acid, lauryl ester of 3-(p-methoxy)phenylmercapto propionic acid, lauryl ester of 3-cyclohexylmercapto propionic acid, lauryl ester of 3-hydroxymethylmercaptopropionic acid, octyl ester of 3-methoxymethylmercaptopropionic acid, dilauryl ester of 3-carboxylmethylmercapto propionic acid, dilauryl ester of 3-carboxypropylmercapto propionic acid, dilauryl-4,7-dithiosebacate, dilauryl-4,7,8,1 l tetrathiotetradecandioate, dimyristyl-4,l l-dithiotetradecandioate, lauryl-3-benzothiazylmercaptopropionate. Preferably the esterifying alcohol is an alkanol having to 18 carbon atoms. Other esters of beta thiocarboxylic acids set forth in Gribbins US. Pat. No. 2,519,744 can also be used.

Likewise, there can be included 0.0ll0%, usually 0.1-5% in the monoolefin polymer formulations polyvalent metal salts. Examples of such salts are calcium stearate, zinc caprylate, calcium 2-ethylhexoate, calcium octate, calcium oleate, calcium ricinoleate, calcium myristate, calcium palmitate, aluminum stearate, calcium laurate, barium laurate, barium stearate, magnesium stearate, as well as zinc stearate, cadmium laurate, cadmium octoate, cadmium stearate and the other polyvalent metal salts of fatty acids set forth previously.

There can also be added phenolic antioxidants in an amount of 0.0ll0%, preferably 0.055%. Examples of such phenols include 2,6-di-t-butyl-p-cresol (Ionol), butylated hydroxyanisole, propyl gallate, 4,4- thiobis(6-t-butyl-m cresol), '4,4-cyclohexylidene diphenol, 2,5-di-t-amyl hydroquinone, 4,4-butylidene bis(6-t-butyl-m-cresol), hydroquinone monobenzyl ether, 2,2-methylene-bis (4-methyl-6-t-butylphenol) (Catalin l4), 2,6-butyl-4-decycloxyphenol, 2-t-butyl-4- dodecycloxyphenol, 2-t-butyl-4-dodecyloxyphenol, 2- t-butyl-4-octadecyloxyphenol, 4,4'-methylene-bis(2,6- di-t-butyl phenol), p-aminophenol, N-lauryloxy-pamino-phenol, 4,4-thiobis( 3-methyl-6-t-butylphenol bis [o-(l,1, 3,3-tetramethylbutyl)phenol] sulfide, 4-acetyl-beta-resorcylic acid, A stage p-t-butylphenolformaldehyde resin, crotonaldehyde condensate of 3-methyl-6-t-butyl-phenol, 2,6-di-t-butyl p-cresol (Ionol), 2,2-methylene bis 4-ethyl-6-t-butylphenol (AG-425), 4-dodecyloxy-2-hydroxy-benzophenone, 3-hydroxy-4-(phenylcarbonyl) phenyl palmitate, ndodecyl ester of 3-hydroxy-4-(phenylcarbonyl) phenoxyacetic acid, and t-butylphenol.

The use of epoxy compounds in an amount of -0.0l5% in the monoolefin and other polymer compositions is also valuable. Examples of such epoxy compounds include epoxidized soya bean oil, epoxidized lard oil, epoxidized olive oil, epoxidized linseed oil, epoxidized castor oil, epoxidized peanut oil, epoxidized corn oil, epoxidized tung oil, epoxidized cottonseed oil, epichlorohydrin'bisphenol A resins (epichlorohydrindiphenylolpropane resins), phenoxy-propylene oxide, butoxypropylene oxide, epoxidized neopentylene oleate, glycidyl epoxystearate, epoxidized alpha-olefins, epoxidized glycidyl soyate dicyclopentadiene dioxide, epoxidized butyl tallate, styrene oxide, dipentene dioxide, glycidol, vinyl cyclohexene dioxide, glycidyl ether of resorcinol, glycidol ether of 1,5-dihydroxynaphthalene, epoxidized linseed oil fatty acids, allyl glycidyl ether, butyl glycidyl ether, cyclohexane oxide, 4-(2,3- epoxypropoxy) acetophenone, mesityl oxide epoxide; 2-ethyl-3-propyl glycidamide, glycidyl ethers of glycerlne, pentaerythritol and sorbitol, and 3,4- epoxycyclohexane-l 1 -dimethanol bis-9,10- epoxystearate.

The ultraviolet light stabilizer can be readily incorporated into the polymeric material by various standard procedures. In one technique, the dry stabilizer in powdered form is mixed with a powdered or granular plastic and the mixture is then appropriately treated by molding or extruding. In another procedure the ultraviolet stabilizer is dissolved in a suitable solvent and the solution is mechanically mixed with the powdered polymer in an open container. Mixing is continued until the solvent evaporates leaving a dry powder which can be molded or extruded by the usual methods.

Significant stabilization is achieved when the ultraviolet stabilizer is used at the one part per hundred resin level, although higher and lower levels are also effective, e.g., from 0.05-10%, usually 0.1-5%.

Unless otherwise indicated, all parts and percentages are by weight.

EXAMPLE I Pentaerythritol Tetrakis (3,4-dimethoxybenzoate) A mixture of 30.0 gms (0.15 mole) of 3,4- dimethoxybenzoyl chloride and 5.11 gms (0.0375 mole) of pentaerythritol was stirred at C. and reduced pressure (15 mm Hg) for 6 hours. The product was a yellow, glassy material which was dissolved in benzenemethanol (1:1) and the solution was then refluxed for 20 minutes. Concentration gave a glassy residue which was crystallized by trituration with ethyl ether. Recrystallization from methanol-benzene (2:1.25) gave a white crystalline powder, mp 160162C., 57% yield. The infrared spectrum was consistent with the structure of pentaerythritol tetrakis (3,4-dimethoxybenzoate) having no hydroxy band and an ester carbonyl band at 5.80p.. The proton magnetic resonance spectrum and carbon-hydrogen analysis agreed with the structure of the tetraester.

EXAMPLE II Pentaerythritol Monostearate Tris(3,4-dimethoxybenzoate A mixture of 16.41 gms (0.0336 mole) of pentaerythritol monostearate and 20.8 gms (0.104 mole) of 3,4- dimethoxybenzoyl chloride was stirred at 100C. and reduced pressure (15 mm Hg) for 5 /2 hours. The mixture was then stirred with methanol for 20 minutes. Removal of the methanol by means of rotary evaporation at reduced pressure gave a waxy product which melted near 35C. and was slightly yellow.

The infrared spectrum was consistent with the structure of pentaerythritol monostearate tris (3,4-dimethoxybenzoate) with two strong carbonyl bands at 5.75 and 5.82p.. The proton magnetic resonance spectrum agreed with the structure:

CHO

wherein n=2.6 and y=l.4.

EXAMPLE III Methyl-a-D-glucoside Tetrakis( 3 ,4-dimethoxybenzoate) Using the same procedure as described in Example I, 3,4-dimethoxybenzoyl chloride was allowed to react with methyl-a-D-glucoside in the molar ratio of 4:1. The reaction was fast and exothermic and gave a 46% yield of a white crystalline compound mp 9496C. The compound gave a negative Beilstein test for halogen and the infrared spectrum confirmed the product was the tetraester with no hydroxyl band and a carbonyl band at 5.8511(5).

EXAMPLE IV Pentaerythritol Tetrakis(2,4-dimethoxybenzoate) Using the procedure of Example I, 2,4- dimethoxybenzoyl chloride was allowed to react with pentaerythritol in the molar ratio of 4:1. The reaction gave a 78% yield of white crystalline product having a melting point of l25126.5C. and the infrared spectrum was a consistent with the expected tetraester with no hydroxyl band and an ester carbonyl band at 5.85,u.(s).

EXAMPLE V EXAMPLE VI 1,2-Bis( 3 ,4-dimethoxybenzamido) benzene Stoichiometric amounts of 3,4-dimethoxybenzoyl chloride (0.10 moles) and o-phenylenediamine (0.05 moles) (molar ratio 2:1) were refluxed for three hours in benzene solution using a 50% excess of triethylamine (0.15 moles) as an acid acceptor. The reaction mixture was filtered and the filter cake stirred with water, washed, and dried. After drying in a warm vacuum oven over 2 hours the product was obtained as white crystals, mp 19ll92C., 90% yield. The infrared was consistent with the expected diamide having amide bands at 3.04 (s,N-I-I) and 6.13 (5).

EXAMPLE VII Pentaerythritol butoxybenzoate) Following the procedure of Example I, 3-methoxy-4- butoxybenzoyl chloride was allowed to react with pentaerythritol in the molar ratio of 4:1. The tetraester was obtained in yield as a white crystalline material, mp 48?50C, which gave a negative Beilstein test for halogen. The infrared spectrum is consistent with the expected tetraester with an ester band at 5.8 1.. The proton magnetic resonance spectrum is also consistent with the title compound.

Tetrakis( 3-methoxy-4- EXAMPLE VIII Pentaerythritol octoxybenzoate) The reaction of thionyl chloride with 3-methoxy-4- octoxybenzoic acid (molar ratio 1:1) gave the acid Tetrakis( 3-methoxy-4- chloride in 93% yield distilled, bp 202C. at l mmof Hg. The infrared spectrum showed the acid chloridecarbonyl band at 5.7p.(s). The 3-methoxy-4- octoxybenzoyl chloride was allowed to react with pentaerythritol according to the procedure of Example I in a molar ratio of 4:1. The product was obtained in 90% yield as white crystals, mp 7476C. The infrared spectrum showed an ester carbonyl at 58,11. and the proton magnetic resonance spectrum was consistent with the title compound. Carbon and hydrogen analysis gave good agreement with the calculated values for the title compound.

EXAMPLE IX 1,1,1-Trimethylolethane Tris( 3 ,4-dimethoxyben zoate) Following the procedure of Example I, 3,4- dimethoxybenzoyl chloride was allowed to react with 1,1,1-trimethylolethane in the molar ratio of 3:1. The product was obtained in 90% yield as a glassy substance which slowly crystallized after being precipitated from methanol at dry-ice temperature. The triester is a white crystalline material, mp l05l06 C., with an ester carbonyl band at 5.85 t. The proton magnetic resonance spectrum was consistent with the title compound.

EXAMPLE X The products of Example I, pentaerythritol tetrakis (3,4-dimethoxybenzoate) and Example 11, pentaeryth ritol monostearate tris(3,4-dimethoxybenzoate), were tested to determine their ability to stabilize polypropyl-.

ene against ultraviolet light degradation. The ultraviolet stabilizer was dissolved in methylene chloride and stirred with powdered polypropylene in an open container. The mixture was stirred until all the solvent evaporated leaving a dry white powder which was com-,

pression molded into panels 0.0312 inch thick. The panels were then exposed to an unfiltered mercury arc lamp (medium pressure, 2537 A). The samples were tested for embrittlement by bending them 180 around a 0.200 inch radius of curvature. Fracture during bending was taken as failure. Results of the test are given in Table I.

I TABLE I STABILIZATION OF POLYPROPYLENE TO HIGH ENERGY (2537 A) ULTRAVIOLET LIGHT Ultraviolet Stabilizer Come. to Embrittlement in phr (Fracture) Pentaerythritol tetrakis (3 ,4-dimethoxybenzoate) 1.0 600 Pentaerythritol monostearate tris( 3 ,4-dimethoxybenzoate) 1.0 48 No Ultraviolet Stabilizer Added (Control) 0.0 24

EXAMPLE XI The ultraviolet stabilizers described in Examples I and 111 through IX as well as several other stabilizers within the invention were tested to determine their ability to stabilize polypropylene against ultraviolet light degradation when exposed in a Weather-Ometer with a Sunshine carbon arc and Corex D filter. Results of the test are given in Table II. The polypropylene panels were prepared by dissolving the ultraviolet stabilizer in a suitable solvent such as methylene chloride and stirring with powdered polypropylene (Profax 6501) in an open container. The mixture was stirred until all the solvent evaporated leaving a dry white powder which was compression molded into panels 0.050 inch thick. The panels were then exposed in a Weather-Ometer. The panels were tested for embrittlement by bending them 180 around a 3/16 inch diameter mandrel. Fracture during bending was taken as failure.

TABLE II WEATHER-OMETER EVALUATION OF ULTIIEIIEYISOLET STABILIZERS lN POLYPROPYLENE Hours to Color at Ultraviolet Stabilizer Conc. in phr Failure Failure 1. None (control) 0 51. yellow 2. Pentacrythritol tetrakis (3,4-di- 1 200 $1. yellow methoxybenzoate) 3. Pentaerythritol tetrakis (3,4-di- 2 500 $1. yellow methoxybenzoate) 4. Pentaerythritol tetrakis (3,4-di- 3 400 yellow methoxybenzoate) 5. Pentaerythritol tetrakis (2,4dil 300 51. yellow methoxybenzoate) 6. l,2-Bis( 3,4-dimethoxybenzamido) 1 200 yellow benzene 7. Pentaerythritol tetrakis(3,5-di- 1 150 yellow methoxybenzoate) 8. Pentaerythritol tetrakis(3-methoxy-4- 1 150 51. yellow butoxybenzoate) 9. Pentaerythritol tetrakis(3-n 1etho Xy-4- 1 $1. yellow octoxybenzoate) TABLE II C0ntinued WEATHER-OMETER EVALUATION OF ULTRAVIOLET STABILIZERS lN POLYPROPYLENE PANELS Hours to Color at Ultraviolet Stabilizer Conc. in phr Failure Failure 10. Methyl-a-D-glucoside tetrakis(3,4- l 175 sl. yellow di-methoxybenzoate) l l. Methyl 3,4-dimethoxybenzoate l 200 sl. yellow l2. 1,] ,l-Trimethylolethane tris(3,4- l 100 sl. yellow di-methoxybenzoate) 13. PETV (0.3 phr DISDAP; 0.05 phr lrganox) l 300 sl. yellow [4. PETV (0.15 phr DISDAP; 0.05 phr l 200 sl. yellow lrganox) l5. PETV (0.2 phr DISDAP; 0.05 phr lrganox) l 200 sl. yellow 16. beta (3,4-dimethoxybenzamido)ethyl l 200 yellow veratrate l7. pentaerythritol tetra(2,4-methylenel 300 sl. yellow dioxybenzoate) 18. 1,1 ,l-trimethylolpropane tris(3,4- l 200 yellow methylenedioxybenzoate) l9. l,l,l-trimethylolethane tris(3,4- l 200 yellow methylenedioxybenzoate) 20. t-butyl veratrate l 200 yellow 21. N,N 3,4-dimethoxybenzoyl) l 200 yellow 1,2-cyclohexane diamine The Weather-Ometer tests described in connection Weather-Ometer tests are set forth in Table III.

with Example XI were carried out with another series In tables I, II and III unless otherwise indicated there of ultraviolet light stabilizers and Profax 6501. Since it was present in the polypropylene 0.15 parts of DISDAP is impossible to reproduce conditions exactly in sepaand 0.05 parts of lrganox 1010. rate Weather-Ometer tests it is necessary to run a blank The monolefin polymers and polyolefins polymers for comparison. The results in this second series of employed in the present invention are solids.

TABLE III WEATHER-OMETER EVALUATION OF ULTRAVIOLET STABILIZERS IN POLYPROPYLENE PANELS Ultraviolet Stabilizer Conc. in phr Hours to Color at Failure Failure No UV Stabilizer Added- Control 0 sl. yellow 1. Pentaecrythritol tetra(3,4-

dimethoxybenzoate l 300 sl. yellow 2. Pentaerythritol tetra(3,4-

methylenedioxybenzoate) l 300 sl. yellow 3. Methyl 2,4-dimethoxybenzoate (liquid) l 300 brown 4. l ,2-Bis(3,4-dimethoxybenzamido) benzene l 200 yellow 5. 1,] ,l-Trimethylolpropane tris(3,4- I

methylenedioxybenzoate) l 200 yellow 6. 1,1 ,l-Trimethylolethane tris(3,4-

methylenedioxybenzoate) l 200 yellow 7. t-butyl 3,4-dimethoxybenzoate (liquid) 1 200 yellow 8. N,N '-3 ,4-dimethoxybenzoyll ,2-

cyclohexanediamine l 200 yellow 9. beta( 3,4-dimethoxybenzamido) ethyl veratrate l 200 yellow 10. 1,2-Cyclohexanediol diveratrate l 200 sl. yellow 1 l. Pentaerythritol tetra(2,4-

dimethoxybenzoate) l 175 sl. yellow 12. Methyl-alpha-D-glucoside tetra (3,4-dimethoxybenzoate) l sl. yellow l3. N-octyl-3,4-dimethoxybenzamide l 150 yellow [4. Pentaerythritol tetra( 4-methoxybenzoate) l 150 $1. yellow Using the procedure described in Example 1 there i 8 were prepared ultra violet stabilizers as set forth 1n the 2 R following table.

TABLE IV Preparation of Experimental Ultraviolet Stabilizers m.p. Exp. Alcohol or Amine Acid Chloride Product Yield C.

l pentaerythritol 0.050 mole 3,4 -methylenedioxybenzoyl F 0.20mole pentaerythritol s 99 225- tetra( 3,4-methylene- 227 dioxybenzoate) 2 0.050 mole 4-methoxybenzoyl 0.20 mole pentaerythritol 93 66.5- tetra(4-methoxy- 68 benzoate) 3 0.022 mole p-dimethylaminobenzoyl 0.088 mole pentaerythritol 41 204- tetra(p-dimethylamino- 206 benzoate 4 methyl-a-D-glucose 0.025 mole 3,4-dimethoxybenzoyl 0.l mole methyl-a-D-glucose 41 94- tetra( 3,4-dimethoxy- 96 benzoate) 5 glycerol 0.033 mole 0.100 mole glycerol tris(3,4- 67 I- dimethoxybenzoate) l2] 6 ethylene glycol 0.05 mole 0.10 mole ethylene-glycol bis 80 I I3- (3.4-dimethoxybenz'oate) l 14 7 meso-erythritol 0.025 mole 0.10 mole meso-erythritol tetra 85 I58- (3,4-dimethoxybenzoate) I59 8 1,2-dihydroxy- 0.05 mole 0.10 mole benzene i l,2-Bis(3,4dimethoxy- 87 16]- benzoxy) benzene 163 9 tert-butanol 0.10 mole 0.10 mole tert-butyl 3,4-dimebp thoxybenzoate l 21- 125 I0 Z-aminoethanol 0.050 mole 0.10 mole 2-(3,4-dimethoxybenz- 72 I- amido) ethyl,3,4-di- 136 methoxybenzoate l l octylamine 0.20 mole 0.20 mole N-octyl-3,4-dimethoxy- 83 8 l-82 benzamide l2 LZ-cyclohexanediol 0.050 mole 0.10 mole 1,2-cyclohexanediol 67 147- Bis( 3,4-dimethoxy- 157 benzoate) l3 1,2-diaminocyclo- 0.05 mole 0.10 mole N,N'-Bis(3,4-dimethoxy- 86 220- hexane benzoyl )-l ,Z-diamino- 227 cyclohexane l4 l,l,l-trimethylol- 0.062 mole 3,4-methylenedioxy- 0.186 mole l,l,l-trimethylolpro- 89 90-93 propane benzoyl pane tris(3,4-methylenedioxybenzoate) 15 1,1 ,l-trimethylol- 0.088 mole 0.264 mole l,l,l-trimethylolethane 90 I02- ethan e tris (3,4-methylenedioxybenzoate) i (Ra where R is alkoxyphenyl, dialkoxyphenyl or alkylene dioxyphenyl, the alkoxy groups having 1 to 8 carbon atoms, and the alkylene group having 1 to 4 carbon atoms, q is 1 to 4, Z is 2 HC-OR O-CH where R is lower alkyl and G is H or R is hydrocarbyl N is 0 or 1 and where at least one of the ns must'be zero;

where s is l to 3 and t is from 0 to 2, the total of s and I being not over 3;

where v and w are each 1 to 4 and p is 2 to 4;

(d) (NH2)' (Mmwhere x is 2 to 3;

(h) alkoxy of l to 18 carbon atoms;

(i) NHR where R is l to 18 carbon atom alkyl or H;

where Y is O-, R -O- where R is alkylene l to 3 carbon atoms,

andfis 2 to 4.

2. A composition according to claim '1, wherein the polymer consists of carbon and hydrogen.

3. A composition according to claim 2, .wherein the polymer is a monoolefin homopolymer, a copolymer of monomers consisting of a plurality of monoolefins or an ethylene-propylene-non conjugated polyene terpolymer. 7

4. A compositionaccording to claim 3, wherein the polymer is polypropylene.

5. A composition according to claim 1 wherein Z is (a).

6. A composition according to claim 1 wherein Z is (b) and t is zero and s is 2.

7. A composition according to claim 1 wherein Z is 8. A composition according to claim 1 wherein Z is (d).

9. A composition according to claim 8 wherein t is zero and s is 2. v

10. A composition according to claim 1 wherein Z is (e).

11. A composition according to claim 10 wherein t is zero and s is 2.

12. A composition according to claim 1 wherein Z is (f).

13. A composition according to claim 12 wherein R is ethylene.

14. A composition according to claim 1 wherein Z is (g)- 15. A composition according to claim 1, wherein Z is (h).

16. A composition according to claim 15 wherein the alkoxy group has 1 to 8 carbon atoms.

17. A composition according to claim 1 wherein Z is (i).

. 18. A composition according to claim 17 wherein R is alkyl, of 1 to 18 carbon atoms.

19. A composition according to claim 1, wherein Z is (j) 20. A composition according to claim 1 wherein Z is (a) and R is methyl.

21. A composition comprising a member of the group consisting of solid monoolefin polymers and solid polyolefin polymers containing a stabilizingly effective amount of a compound having the formula where R is dialkoxyphenyl or alkylene dioxyphenyl, the alkoxy groups having 1 to 8 carbon atoms and u is 2 to 4.

22. A composition according to claim 21 wherein both R groups are dialkoxyphenyl.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,888,823 Dated June 10, 1975 Inventor(s) Robert G. Gough It: is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Certificate of Correction Under Rule 323 Column 14, line 15, change "polyethylene" to --polypropylene--.

Column 18, line 43, change "N" to --n Column 19, line 10, rewrite the formula as follows:

. ORII III Column 19, line 22, change "for" to --form=--.

Signed and Scaled this twenty-eight D ay Of October 1 975 [SEAL] A ttes t:

RUTH C. MASON C. MARSHALL DANN Attesting Officer Commissioner ufParenls and Trademark: 

1. A COMPOSITION COMPRISING A MEMBER OF THE GROU CONSISTING OF SOLID MONOOLEFIN POLYMERS AND SOLID P MERS CONTAINING A STABILIZINGLY EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA
 2. A composition according to claim 1, wherein the polymer consists of carbon and hydrogen.
 3. A composition according to claim 2, wherein the polymer is a monoolefin homopolymer, a copolymer of monomers consisting of a plurality of monoolefins or an ethylene-propylene-non conjugated polyene terpolymer.
 4. A composition according to claim 3, wherein the polymer is polypropylene.
 5. A composition according to claim 1 wherein Z is (a).
 6. A composition according to claim 1 wherein Z is (b) and t is zero and s is
 2. 7. A composition according to claim 1 wherein Z is (c).
 8. A composition according to claim 1 wherein Z is (d).
 9. A composition according to claim 8 wherein t is zero and s is
 2. 10. A composition according to claim 1 wherein Z is (e).
 11. A composition according to claim 10 wherein t is zero and s is
 2. 12. A composition according to claim 1 wherein Z is (f).
 13. A composition according to claim 12 wherein RIV is ethylene.
 14. A composition according to claim 1 wherein Z is (g).
 15. A composition according to claim 1, wherein Z is (h).
 16. A composition according to claim 15 wherein the alkoxy group has 1 to 8 carbon atoms.
 17. A composition according to claim 1 wherein Z is (i).
 18. A composition according to claim 17 wherein R9 is alkyl, of 1 to 18 carbon atoms.
 19. A composition according to claim 1, wherein Z is (j).
 20. A composition according to claim 1 wherein Z is (a) and R12 is methyl.
 21. A composition comprising a member of the group consisting of solid monoolefin polymers and solid polyolefin polymers containing a stabilizingly effective amount of a compound having the formula
 22. A composition according to claim 21 wherein both R14 groups are dialkoxyphenyl. 